Manufacture of phosphoric acid and other products from phosphatic material



Sept. 5, 1933. J. w. WALTON 1,925,510

MANUFACTURE OF PHOSPHORIC ACID AND OTHER PRODUCTS FROM PHOSPHATIC MATERIAL Original Filed March 23, 1929 2 Sheets-Sheet l M er-e Q Washer Bol 1e!" Qn 906 bu FY12 r* and gas burner" INVENTOR F {3411 68 J1 AT oRNEYS p 5, 1933- J. w. WALTON MANUFACTURE OF PHOSPHORIC ACID AND OTHER PRODUCTS FROM PHOSPHATIC MATERIAL Original Filed March 23, 1929 2 Sheets-Sheet 2 v orc w IxDzQDDz @kNnEG O QCEUQ Nm E i QM (R b 15 wL rl Er. T UW I NVEN'I'OR Patented Sept. 5, 1933 1,925,510 I nannraornas or rno srnoiuo com AND OTHER MATERIAL PRODUCTS FROM PHOSPHATIC John William Walton, Roclsdale, Tenn'., assignor a to Tennessee Products (Jorporation, Nashville, Tenn, a corporation of Tennessee Original application March 23, 1929, Serial Nor 349,328. Divided and this application May 28, 1936*. Serial No. 456,448.

Claims.

This invention relates to the manufacture of phosphatic and other products from phosphatic,

smelting, in a blast or other type of furnace, of

. phosphatic material, iron bearing material, fluxing agents and carbon, in sucha manner, and

under such control, as toevolve'or give ofi gases which are suitable for treatment to recover therefrom elemental phosphorus, phosphoric anhydrid, phosphoric acid, polishing powders, fertiizers and othercornrnercial products.

The invention consists substantially in the mode of operation, control, treatment and products, alias, will be more fully hereinafter set forth, as illustrated in the accompanying drawings and finally set forth in the appended claims.

r 'erring to the accompanying drawings,- Figure lis'a view, parts in vertical section illustrating somewhat diagrammatically a furnace of the blast furnace type and auxiliary connections I for drawing off and treating the gases evolved during the smelting operation carried on in said furnace.

Fig. 2 is a diagrammatic view illustrating apparatus for treating the gases drawn oil from the fusion zone of the furnace.

The subject-matter herein set forth, described and claimed is divided out from my application re ial No. 349,328, filed March 23, 1929.

the operation of blast or other types of fuel fired furnaces in the manufacture of phosphids of iron, such, for example, as the product known -o--phcsphorus,' as heretofore ordina ily carut, phosphatic material, iron bearing mate rial, carbon and suitable rluxing agents are charged into the top of the furnaceand the stack or is ignited at the base, a blast of heated bei supplied into the furnace near its base to maint in combustion of the carbon content of the m or ed prod lots of the combustion which rise through the stack or pile of material, heats the iron bearing material and tends to reduce the iron con'- The object of the invention issto carry on the The gases generated and other heattained therein to the metallic state, as the mass descends throughsthe furnace, and the heat generated at the base of the furnace tends to liberate phosphorus gases from the phosphatic material charged into the. furnace. The liberated phosphorus gases react with the free carbon in the presence of the heat createdv to release elemental phosphorus from said gases. This liberated phosphorus then reacts with the reduced metallic iron to produce iron phosphid, such as form-phosphorus, which drips down into a chamher at the base of the furnace to form a molten pool which is tapped off to form the commercial product. At the same time a molten slag also accumulates in a pool which overlies the ferro-phosphorus pool, and this molten slag is likewise drawn off and treated to produce commercal products, or is otherwise disposed of.

[While it has been ,known that the gases and other products of cornbustion'evolved and given off during the smelting operations carried on in the furnace, contain valuable properties and constituents, and especially valuable quantities of phosphorus in various forms of compounds, no

serious eifort, so far as I am aware, has heretofore been directed towards the recovery, and utilization of said properties and constituents in the form of commercial products, nor have any efforts been made to regulate or control the smelting operations carried on in the furnace so as to generate or evolve and give off gasesv or other combustion products of such enhanced or enriched quality, character or content as to render the furthertreatment thereof for the recovery of such content an advantageous and profitable enterprise. a

My present-invention relates more particular- 1y to the control and regulation of the smelting operations and of thegeneration ofphosphorus gases and compounds, and other contents of such gases, evolvedduring the smelting operations in a blast furnace, and the withdrawal'of the said gases from the furnace at the proper time, and from the proper points whereby to produce efficiently and economically gases which are rich .in phosphorus and other compounds and substances andv of a nature and character to be easily, efilciently and economically extracted or recovered therefrom as commercial products, such as elemental phosphorus, phosphoricacid, poll ,ng powder, fertilizers'and other products. .l also propose to control and regulate the smelting operations carried on in a blast furnace, using the necessary raw materials, so as to produce gases having the necessary properties or contents for treatment as above pointed out, whether the smelting operations are carried out primarily for the production of such gases, and any iron phosphid produced being a by-product of the operation, or whether iron phosphid, or ferro-phosphorus is the primary product and the gases, and other products obtained therefrom are lay-products. In either or any case the present invention deals with the operations, and the control and regulation thereof, for producing, as commercial products, elemental phosphorus, phosphoric acid, fertilizers, powders, etc. from gases evolved in smelting phosphatic material and iron bearing material with carbon and suit able fluxing agents, in a blast furnace.

I have discovered that in smelting phosphatic ores, or material, with iron bearing material in a blast furnace, distinctively different characters and qualities of gases may be obtained according to the point in the furnace from which such gases are drawn off. Thus, the gases taken or drawn off from near the top of the furnace, particularly where the amount of phosphatic content of the material employed is relatively small, generally carry only a small quantity of phosphorus or phosphorus compounds, and such gases also generally contain a large amount of impurities derived from the materials which are charged into the furnace.

It is my belief that these impurities are, in large part, carried mechanically in the gases, and are produced by the attrition or friction of the gases upon the particles of raw materials charged into the furnace as the gases are forced through the mass of said material at a rapid speed. I base this belief upon the fact that the impurities are usually carried along with the gases in a finely divided state. These gases, drawn from the top of the furnace are ordinarily utilized in various of the accessory appliances employed in the operation of the furnace, such as in the hot blast stoves which pre-heat the air blast supplied to the furnace; in heating the boilers of the power equipment, and for various other purposes. The presence of these impurities in the gases tend to clog up and obstruct the pipes and passages through which the gases travel. This very seriously interferes with the efficient and economical operation of the furnace and plant as a whole, and hence exerts an injurious effect in the generation of the phosphorus bearing gases and compounds.

On the other hand, I have discovered that the gases produced and existing in the lower and hotter portions of the furnace, when withdrawn from the region in which they are produced, are not only comparatively free from impurities in a finely divided state carried along mechanically by the gases, but they are also richer in phosphorus, as well as in phosphorus pentoxid (P205), as compared with gases drawn off from the top of the furnace.

It is my belief that the reason for this difference in the nature and character of the gases drawn from the two different points of the furnace referred to, is that in a blast furnace in which iron bearing ore or material, and'phosphatic ore, rock or material are smelted, two melting zones are produced. The phosphatic ore or material requires a much higher fusing temperature than does iron, limestone, silica, etc. and consequently the gases drawn from the top of the furnace are mainly generated by the fusion of the iron ore or material, the limestone, silica,

etc. and hence are necessarily leaner in phosphorus content, whereas those drawn from the hotter portion of the furnace are produced as a result of a higher temperature and more com plete fusing of the phosphatic material, and con sequently are richer in phosphorus content.

Another explanation of the difierence in character, nature and content of the gases drawn from the two points of the furnace, referred to, according to my belief and experience, is that the reduction of the phosphatic material is facilitated and made more complete by bringing that material into contact With incandescent carbon. Iron oxid, on the other hand, is readily reduced by carbon monoxid gas. The heated gases ascending through the furnace, therefore, appear to effect the reduction of the iron bearing material, at least to a substantial extent, at a considerable distance above the region of the tuyeres where the air blast is supplied into the furnace, and hence, where the greatest degree of heat occurs and where the phosphatic material as well as the carbon attain their highest degree of heat. It is when the phosphatic material and the carbon are in their incandescent state, and are brought together in that state that the phosphatic material is more easily, readily and com-- pletely reduced. Consequently, the gases generated and existing in the furnace in and near the hottest point or fusion zone, namely, in the region of the tuyeres, are much richer in phosphorus content, than are those drawn from the top of the furnace. Moreover, the gases generated and existing in the region of the fusion zone do not have the same opportunity to gather up and carry with them fine particles of material rubbed from the ore, carbon,'etc. as do the gases which ascend through the pile or mass of the material to be drawn off from the top of the furnace, and hence the gases in the fusion zone are comparatively free from such mechanically carried particles and other impurities.

While therefore, within the broadest scope of my invention, I may draw off the gases generated within the furnace from either the top of the furnace stack, or from the fusion zone, or from any other desired point, and treat them for the recovery of the valuable constituents thereof, I prefer, in practice, to separately draw off the gases from the top and from the fusion zone of the furnace, according to the nature of the par-- ticular content of the gases that is tobe recovered therefrom by the subsequent separate treatment thereof, thereby enabling me to take full advantage of the different natures and characteristics of the gases in the recovery of the valuable constituents of the same.

I have also discovered that by drawing of gases from the fusion zone or hottest part of the fur nace, with or without drawing also from the top of the furnace, conditions are created in the fursaid products also are to be produced, whether as primary products or as by products incidental to the production of the desired gases. The nature and quality of the ferro-phosphorus and slag products affects and controls to a large extent the nature and quality of the gases. This enrichment of the gases, and enhanced quality of the ferro-phosphorus and increased fusibility of the slag product, I believe to be due in a large measure to the better and more perfect and complete fusion of the materials, and more perfect and complete metallurgical and chemical reactions, which take place, by withdrawing a portion of the gases from the fusion zone of the furnace. 1 base this belief on the fact that by withdrawing more or less of the gases, particularly those-generated or evolved and existing in the region or the tuyeres, and the same thing holds true to a more or less extent, also, with regard to gases drawn off from the top of the furnace, opportunity is permitted to increase the supply of air blast through the tuyeres, thereby securing better conditions within the furnace for carrying on the fusion and combining reactions.

accelerates the combining reactions which take place in the furnace, resulting, in practice in the attainment of a higher temperature in a shorter space of time than heretofore, and consequently, permits a reduction in the quantity of carbon reuired, which is one of the most expensive of the materials charged into the furnace, without, however, preventing the presence and mantenance of sufficient free carbon in the fusion zone to accomplish the desired reactions. This se cures greater economy as well as a richer gaseous product, and also a higher grade of ferro-phosphorus and a more fusible slag product.

In the practical operation of the furnace, in carrying out my invention, itis necessary to take into consideration various factors in order to secure the best results. The burden charged into the furnace should be composed of clean, high grade materials of the best quality. The various materials charged should be properly proportioned and balanced as between themselves, and maintained in that proper balance in the successive charges. Should an unbalanced condition of burden occur, the ordinary furnace man of experience, by well known methods, can readily and easily ascertain in what direction the unbalance occurs, and then take the proper steps to restore the balance. If the burden is found to be too lean or too limey, correction is effected by adding or reducing the lime or the silica contents of the charge, as the case may require.

By observing the volume and color of the gases finally escaping into the air from the'top of the furnace stack, and the color of the escaping gases when burned, the experienced furnace man can ordinarily tell when the furnace is operating properly. These visible observations, based on experience, can be easily and readily checked by suitable and proper chemical analysis according to well known and well understood methods. 7

I have found that atmospheric conditions and humidity affect to some extent the fusing conditions and smelting reactions carried onwithin the furnace, and hence, also the character of the evolved gases and other products resulting from said reactions. This is particularly true when working with phosphatic materials. Therefore, in carrying out my invention in the most advantageous and desirable manner, the'working opancing of v the same in the successively charged burdens, but also with respect to the supply of air blast, its dryness and quantity, and the degree to which it is preheated. I'have found in practice that an air blast supply ranging from four thousand-to sixteen thousand cubic feet of 'air per minute, according to the nature, char- 'with' the result that inferior grades of gaseous,

ferro-phosphorous, slag and other products will be produced. If too great a volume of air is supplied, the melting or fusion points will be raised to too great a height within the furnace, thereby resulting in setting free phosphorus pentoxid gases (P205) at a point too high .up in the furnace to enable said gases to properly react with the carbon or to be altered by the carbon into a form enabling them to combine or react with the iron present, and possibly other disadvantages also result from the use of too great or small a volume of air. However, with a properly proportioned or balanced burden of the proper quality and grade of materials, a proper control of the operations of the furnace, and of the air supply, a complete effective and satisfactory fusing and combining reaction is attained, thereby resulting in the generation and evolution of the desired character of gaseous products suitable pending on the various conditions above referred to, and which I have found to be satisfactory in carrying out my invention is as follows:

Pounds Coke (84% carbon) 5200 V Phosphate rock (containing 12% to, say,

17% phosphorus) 4400 Iron ore (containing from 38% to %11'011- 3280 Iron ore tailings (containing from i0% to I or silica and 10% meow, iron) 2400 An air blast of from eight thousand to twelve thousand cubic feet per minute.

It is to be understood, however, that this is'only My invention, therefore, is not to be limited or restricted to the exact proportions given, as such proportions may be varied from throughout a wide range and still the benefits and advantages of my invention realized in whole or in part.

For example, I may replace the whole or part of the iron ore tailings with scrap iron, or other forms of metallic iron. Instead of relying on the silica content of iron tailings for the necessary silica for a fluxing agent, and on the phosphatic 'o r'e having a lime content for the necessary lime for a fluxing agent, I may independently supply lime and silica, either or both, and in the required proportional amounts to constitute the fluxing agents.

It is also to be understood that the phosphorous content of the charge may be derived from other sources than phosphate rock as, for instance, from ferro-phosphorus, off 5-ferrophosphorus, or from other materials. I

In the accompanying drawings I have shown a conventional form of blast furnace suitable for use in carrying out my invention. Generally the furnace consists of a vertical shaft portion A, into the open top of which the material to be treated is charged, the open top being closed, after the charge is introduced, by a bell or other closure B. The shaft portion A, increases in interior area frfom its top towards the bottom thereof. Below the lower end of the shaft portion A, is the portion C, which, usually, is of decreasing interior area, downwardly from its line of junction with the shaft portion A, Within this portion C, occurs what is called the fusion zone in which the principal smelting reactions take place. Near the bottom of the portion (3, are located the tuyeres I), through which air blasts are delivered into the furnace. Below the tuyres are located the chambers F, and E, in which, respectively, collect the molten slag, and iron phosphid or ferro-phosphorus products and from which said molten products may be drawn or tapped off through the notches and G. Communicating with the shaft A, at or near its upper end, is a pipe connection K, ti" gases may be drawn off. Commui eating with the portion 0, of the furnace at or near the vicinity of the tuyres, are one or more outlets or extractors J through which gases evolved and existing in the fusion zone or hottest part of the furnace may be drawn on".

The particular location of these outlets or extractors is not of consequence so long as they are so located as to serve the purpose of drawing off or extracting the gases from the region of the chamber or portion of the furnace where the principal reactions take place, that is, from the region of the zone of the highest temperature and pressure of the furnace.

The material employed in the form of coke, phosphatic material, iron bearing material and lime and silica, as fluxing agents, is charged into the furnace in the manner now well known and practiced. This mass is ignited at the base of the pile and combustion is maintained by the air blast. The heated products of combustion, and the gases evolved and given off tend to ascend, or are driven by the force of the blast through the mass of materials, and, as the combustion and smelting operations proceed, the charged materials descend through the furnace shaft. The descending mass of materials encounters the upward fiow of the heated gases, thereby beginning and carrying on the smelting and other reactions, which are finally completed in the fusion zone. Any slag or iron phosphid produced, collects, in molten condition, in the chambers F, E, and any phosphorus containing or other gases, generated or evolved are drawn off through the pipe connections K, J, one or both.

My present invention is concerned with the gases and gaseous products that are drawn off from the furnace and their treatment for the recovery therefrom of various valuable commercial products.

As hereinabove stated these gases, not only contain fine particles of material derived from the materials charged into the furnace, but also place, and more a larger volume of the fine particles than those drawn off from the fusion zone, while the latter are richer in phosphorus content, due to the more perfect fusing and combining reactions which take place within this portion of the furnace. These gases, whether drawn ofi-from the one point or the other, may be treated in various ways to recover therefrom their valuable constituents. It will be understood that the gases within the furnace in the region of the tuyeres, say in a region roughly defined by the level of the slag in chamber F, upwardly to the top of the bosh, or widest partof the furnace, are subjected to the maximum temperature, and pressure developed in the furnace. The temperature runs, for example, from 2,000" F. to 3,000" F. and the gases are maintained under a pressure of from four pounds, to, say, fifteen pounds above atmospheric pressure. This temperature and pressure to which'tho gases are subjected will vary, somewhat, according to the practical conditions under which the furnace is operated, accordingly the best location of the point from which the gases are withdrawn, can ordinarily be ascertained from practical experience suitable, is to insert one or more pipes J, through the wall of the furnace, the inner ends of said pipes projecting into the furnace and to connect an enlarged drum or mufiier to the outer ends of said pipes. The gases are forced from the interior of the furnace by the pressure under which they are subjected in the furnace, through the pipe J, and into the muffler N. I prefer to deliver into the pipe J, a jet or spray of water or steam. This can be accomplished in various ways. A simple arrangement is to locate a spray jet or head 18, within the pipe connection J and to deliver thereto water or steam under pressure, as, for example through pipe connection 25, from any convenient source. Where water is supplied, it' is instantly converted into steam which becomes superheated from the heat of the gases. The purpose of supplying the water, or steam, is two-fold. In the first place it prevents the pipe connection J from burning out, under the high temperature of the gases, and in the second important, the superheated steam reacts upon the gases in such manner as to cause a deposit of substances upon the inner Wall surface of the pipe connection. This deposit adheres to the surface of the pipe and forms a coating or lining constituting a heat insulation therefor. I have found this coating substance to be composed principally of silica having in admixture therewith varying amounts of elemental phosphorus, red phosphorus and possibly other phosphorus compounds. Just what chemical reactions take place within the pipe connection J, and within the drum or muiiier N, I am unable to say with accuracy but it is my belief that when the hot gases come in contact with the water which has been converted into superheated steam, ammonia, phosphin and other compounds are formed.

In the case of ammonia the nitrogen element ,thereof undoubtedly is obtained from the air and efficient mode, I propose to burn the gases and then to subject the products of combustion to precipitation to produce phosphoric acid. In the illustrative arrangement shown, the pipe 47 from the last of the series of scrubbing chambers 44, delivers into a suitable combustion chamber P, in which the gases are burned, to reniovethe carbon monoxide and other inflammable gases therefrom, and to oxidize any elemental phosphorus to phosphorus pentoxid; From the cornbustion chamber the resulting gaseous products, after being cooled down to a suitable temperature of, say, from to 110 F., are delivered into and subjected to the action of a precipitator B. This precipitator may be of any desired coinrnercial type,'such, for example, as an electrical precipitator of the Cottrell type. The resulting precipitate, phosphoric acid, is then drawn for commercial use or sale, or such. further refinement as may be necessary or required.

The heat developed by the burning of the gases in the combustion chamber P, may be utilized for any desired purpose.

Where the gases generated and evolved in the furnace, and other products ofcombustion, are drawn off from the top of the furnace instead of from the fusion zone, they may be treated in the same manner as abovedescribed for the recovery therefrom of elemental phosphorus, phosphoric acid and fertilizer material; However, and as above pointed out, where said gases and gaseous products are drawn off from the top of the fur nace, they carry along with them particles of dust and other fines from the burdens charged into the furnace.

This is true whether all the gases are drawn off from the top of the furnace instead of from the fusion zone, or'whether they are drawn off from both points. I have discovered that the fines, dust and the like, so carriedalong, with the gases contain carbon, silica, alumina, lime, potash, iron oXid, phosphorus pentoxid and perhaps other materials, which, in combination, or in admixture with each other, constitute a valuable cleansing and polishing agent in the form of a powder which is unctious, impalpable and free from crystaline particles. This powder can be separated out from the gases in various ways, and collected and packaged as a commercial article for sale or use. In practice I have found it convenient, practical and efiicient to preliminarily catch and separate out from the gases the larger particles of dust, carbon and the like, and then treat the gases which retain the finer particles. Such treatment, in one practical mode, consists in burning the gases, usefully employing, in any desired way, the heat developed by the burning operation, and finally precipitating the dust, fines, etc. from the products of combustion.

In the drawings, Fig. 1, I have shown an arrangement in which the gases are drawn from the fusion zone and also from the top of the furnace, and I have above pointed out that the gases drawn from the top of the furnace, are lower in phosphorus content and richer or more heavily laden with dust, fines, etc. than are those drawn from the fusion zone, and in practice I prefer this method of separately drawing off and treating the gases, because of these differences in the characters of the gases when drawn off from these respective pointslalthough, in its broadest scope, my invention is not to be limited or restricted in this respect. 7

As shown, the pipe K, connected'to the top of the furnace delivers into a dust collecting, and

settling chamber S, and thence passes by pipe 50 into and through a washer T, containing water. The larger particles of finescarried along with the gases will settle down in chamber S, or will be caught in the washer T. From the washer the gases are conducted to a boiler V, employed for generating steam, or to a stove W, for preheating the air blast supply to the furnace, or to both of these accessory devices, where said gases are burned. Itis my belief that in burning the'gases only the carbon monoxid, and possibly other inflammable gases, containedtherein are consumed, whereas the dust, fines and the like,

not.

After burning the gases, as above described, the products of combustion are subjected to the action of a precipitator, indicated at O, which may be of the Cottrell electric or any other suitable type, whereby-the fines, dust, etc. are thrown down as a precipitate, in the form of a light grayish to white powder which constitutes a valuable product as a cleansing and polishing agent which may be collected and packaged for sale or use.

A typical analysis of this powder is as follows:

Moisture C.) 2, 00% silica 48. 92% Alumina 16. 46% Lime 12.60% Magnesia I 15%v Manganese oxid .30% Iron oxid 5. 48% Phosphorus pentoxid (P205) 5. 72% Potash (K20) 7. 57% Sodium oxid (NazO) trace Fluorin 80 Carbon; trace Should the dust product after precipitation, be found to contain solid particles, such as carbon, lime or the like, in uncombined condition to any undesirable extent, such foreign and undesirable particles may be readily separated out and removed mechanically by sifting or other well known methods.

From the foregoing description it will be seen that I provide a method of treating phosphatic material, iron bearing material, carbon and fluxing agents in an ordinary blast furnace, and to obtain from such treatment, under proper and suitable conditions of control of the materials employed, and of the operations, gaseous products which contain or carry valuable constituents capable of being recovered therefrom as commercial articles and substances, whether such treatment and operations are carried on for the primary object of obtaining the commercial arti cles and substances, or whether they are obtained as by-products from the treatment and operations primarily designed for the manufacture of other commercial products such as ferro-phosphorus, 1

Havingnow set forth the objects and nature of my invention, and the manner of carrying the same into practical use and operation, what I claim as new and useful, and of my own invention, and desire to secureby Letters Patent isz The process which consists in drawing ofi a portion of the gases rich in phosphorus fromthe combustion zone of a blast furnace charged with phosphatic materials, and delivering a jet of water into the hot gases and at a point closely adjacent that at which they are drawn off, to

deposit from said gases an insulating coating upon the inner walls of the conduit through which they are drawn 0E.

2. The process which consists in drawing of: a portion of the gases rich in phosphorus from the combustion zone of a blast furnace charged with phosphatic materials, and delivering a jet of water'into the hot gases as they are drawn on, then scrubbing or filtering the gases by passing successively through chambers containing water, then burning the scrubbed and filtered gases, and finally precipitating the burned gases to recover phosphoric acid therefrom.

3. The process which consists in drawing off a portion of the gases rich in phosphorus from the combustion zone of a blast furnace charged with phosphatic mater als, and delivering into the gases so drawn on", a jet of Water, then delivering the gases into a settling tank to permit the sludge content thereof to settle out therefrom and returning the supernatant water from the settling tank into the water supply to the withdrawn gases.

e. The process which consists in drawing off a portion of the gases richin phosphorus'from the combustion zone of a blast furnace charged with phosphatic materials, and delivering into the gases so drawn off, a jet of Water, then delivering the gases into a settling tank to permit the sludge content thereof to settle out therefrom, then distilling the settled sludge and adding ammonia and potassium salts to the residue of the distilling operation to form a commercial fertilizer.

JOHN WILLIAM WALTON. 

